CN117321789A - Electrode and battery - Google Patents
Electrode and battery Download PDFInfo
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- CN117321789A CN117321789A CN202280035676.7A CN202280035676A CN117321789A CN 117321789 A CN117321789 A CN 117321789A CN 202280035676 A CN202280035676 A CN 202280035676A CN 117321789 A CN117321789 A CN 117321789A
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- active material
- electrode
- block copolymer
- solid electrolyte
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Classifications
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The electrode 1000 includes an active material layer 110 and a current collector 100, wherein the active material layer 110 includes an active material 112, a solid electrolyte 111, and a binder 113, and the current collector 100 includes a substrate 101 and a coating layer 102 that covers the substrate 101 and contacts the active material layer 110. The adhesive 113 contains a block copolymer including 2 1 st blocks composed of repeating units having aromatic rings and 2 nd blocks located between the 2 1 st blocks. The weight average molecular weight of the block copolymer is 17 ten thousand or more. The coating layer 102 contains conductive carbon.
Description
Technical Field
The present disclosure relates to electrodes and batteries.
Background
Patent documents 1 to 3 disclose an electrode including an active material layer including an active material, a solid electrolyte, and a binder, and a current collector, and a battery using the electrode. In particular, patent document 3 discloses that a conductive carbon film is disposed on the surface of a current collector.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2018-125260
Patent document 2: japanese patent laid-open publication No. 2010-2626764
Patent document 3: international publication No. 2013/108516
Disclosure of Invention
An object of the present disclosure is to provide an electrode suitable for improving the peel strength of an active material layer from a current collector.
An electrode according to one embodiment of the present disclosure includes an active material layer and a current collector,
the active material layer includes an active material, a solid electrolyte, and a binder; the current collector has a substrate and a coating layer that covers the substrate and is in contact with the active material layer,
the adhesive contains a block copolymer comprising 2 1 st blocks composed of repeating units having aromatic rings and 2 nd blocks located between 2 1 st blocks,
the weight average molecular weight of the block copolymer is 17 ten thousand or more,
the coating layer contains conductive carbon.
The present disclosure provides an electrode suitable for improving the peel strength of an active material layer and a current collector.
Drawings
Fig. 1 is a cross-sectional view of an electrode according to embodiment 1.
Fig. 2 is a cross-sectional view of a battery according to embodiment 2.
Detailed Description
(summary of one embodiment of the present disclosure)
The electrode according to embodiment 1 of the present disclosure includes an active material layer and a current collector,
the active material layer includes an active material, a solid electrolyte, and a binder; the current collector has a substrate and a coating layer which is coated on the substrate and is in contact with the active material layer,
The adhesive contains a block copolymer comprising 21 st blocks each comprising a repeating unit having an aromatic ring and 2 nd blocks located between 2 of the 1 st blocks,
the weight average molecular weight of the block copolymer is 17 ten thousand or more,
the coating layer contains conductive carbon.
According to embodiment 1, the active material layer is in contact with the coating layer of the current collector. At this time, the aromatic ring contained in the block copolymer of the binder in the active material layer interacts with the conductive carbon of the coating layer. By this interaction, adhesion between the active material layer and the current collector is improved, and the peel strength between the active material layer and the current collector tends to be improved. As described above, the electrode is suitable for improving the peel strength of the active material layer from the current collector.
In aspect 2 of the present disclosure, for example, in the electrode according to aspect 1, the average polymerization degree of the 1 st block may be 210 or more.
According to claim 2, the peel strength between the active material layer and the current collector can be further improved.
In the 3 rd aspect of the present disclosure, for example, in the electrode according to the 1 st or 2 nd aspect, the 2 nd block may contain a repeating unit derived from a conjugated diene.
According to claim 3, the peel strength between the active material layer and the current collector can be further improved.
In the 4 th aspect of the present disclosure, for example, in the electrode according to any one of the 1 st to 3 rd aspects, the block copolymer may be a triblock copolymer, and the repeating unit having the aromatic ring may include a repeating unit derived from styrene.
According to the 4 th aspect, the block copolymer tends to be soft and have high strength. Therefore, the peel strength between the active material layer and the current collector can be further improved.
In the 5 th aspect of the present disclosure, for example, in the electrode according to the 4 th aspect, the block copolymer may be a hydride.
In the 6 th aspect of the present disclosure, for example, in the electrode according to any one of the 1 st to 5 th aspects, the above block copolymer may contain at least 1 block copolymer selected from the group consisting of a styrene-ethylene/butylene-styrene block copolymer (SEBS), a styrene-ethylene/propylene-styrene block copolymer (SEPS), and a styrene-ethylene/propylene-styrene block copolymer (SEEPS).
According to mode 5 or 6, there is a tendency that the block copolymer is softer and has higher strength. Therefore, the peel strength between the active material layer and the current collector can be further improved.
In the 7 th aspect of the present disclosure, for example, in the electrode according to any one of the 1 st to 6 th aspects, the substrate may include aluminum or an aluminum alloy.
According to claim 7, aluminum and aluminum alloy are lightweight metals having high conductivity. Therefore, according to this electrode, not only the peel strength between the active material layer and the current collector can be improved, but also the gravimetric energy density of the battery can be improved.
In the 8 th aspect of the present disclosure, for example, in the electrode according to any one of the 1 st to 7 th aspects, the active material may contain a transition metal oxide containing lithium.
According to the 8 th aspect, not only the peel strength between the active material layer and the current collector can be improved, but also the average discharge voltage of the battery can be improved while suppressing the manufacturing costs of the electrode and the battery.
In the 9 th aspect of the present disclosure, for example, in the electrode according to the 8 th aspect, the active material may contain lithium nickel cobalt manganese oxide.
According to the 9 th aspect, not only the peel strength between the active material layer and the current collector but also the energy density of the battery can be improved.
A battery according to a 10 th aspect of the present disclosure includes a positive electrode, a negative electrode, and an electrolyte layer between the positive electrode and the negative electrode,
At least one selected from the positive electrode and the negative electrode is an electrode according to any one of aspects 1 to 9.
According to the 10 th aspect, not only the peel strength between the active material layer and the current collector is improved in the electrode provided in the battery, but also excellent output characteristics can be achieved in the battery.
In the 11 th aspect of the present disclosure, for example, in the battery according to the 10 th aspect, the positive electrode may be the electrode.
According to the 11 th aspect, not only the peel strength between the active material layer and the current collector is improved in the electrode provided in the battery, but also more excellent output characteristics can be achieved in the battery.
Embodiments of the present disclosure will be described below with reference to the drawings.
(embodiment 1)
Fig. 1 shows a cross-sectional view of an electrode 1000 according to embodiment 1. The electrode 1000 in embodiment 1 includes a current collector 100 and an active material layer 110. The active material layer 110 includes a solid electrolyte 111, an active material 112, and a binder 113. The current collector 100 has a substrate 101 and a coating layer 102. The coating layer 102 coats the substrate 101 and is in contact with the active material layer 110. The adhesive 113 contains a block copolymer. The block copolymer contained in the adhesive 113 includes 2 1 st blocks composed of repeating units having aromatic rings and 2 nd blocks located between the 2 1 st blocks. The weight average molecular weight of the block copolymer is 17 ten thousand or more. The coating layer 102 contains conductive carbon.
With the above configuration, in the electrode 1000 according to embodiment 1, the active material layer 110 tends to be prevented from being peeled off from the current collector 100. Further, the output characteristics of the battery including the electrode 1000 can be improved. The electrode 1000 may be used, for example, as an electrode of an all-solid secondary battery.
Patent documents 1 and 2 disclose an electrode including an active material layer including an active material, a solid electrolyte, and a binder, and a current collector, and a battery using the electrode. However, with the electrode structures disclosed in patent documents 1 and 2, the peel strength between the active material layer and the current collector cannot be sufficiently improved.
Patent document 3 discloses an electrode including an active material layer including an active material, a solid electrolyte, and a binder, and a current collector, and a battery using the electrode. In particular, patent document 3 discloses that a conductive carbon film is disposed on the surface of a current collector. However, with the structure of the electrode disclosed in patent document 3, the peel strength between the active material layer and the current collector cannot be sufficiently improved.
The inventors of the present application have first noted that the adhesion between the active material layer and the current collector in the conventional electrode is insufficient, and studied the active material layer and the current collector. As a result, the inventors of the present application have found for the first time that the peel strength between the active material layer and the current collector is improved by laminating the active material layer containing a block copolymer having a large molecular weight and having an aromatic ring, and the current collector containing conductive carbon. In this regard, although the detailed mechanism is not clear at this stage, it is inferred that the interaction between the aromatic ring and the conductive carbon contained in the block copolymer has an influence. Examples of the interaction include pi-pi interaction. Further, it is assumed that the plurality of block copolymers are approximately crosslinked by the interaction of blocks composed of repeating units having aromatic rings, which also affects the peel strength of the active material layer and the current collector.
The inventors of the present application have further studied based on the above findings. As a result, it was found for the first time that the peeling strength between the active material layer 110 and the current collector 100 in the electrode 1000 can be improved by laminating the active material layer 110 including a block copolymer including 2 1 st blocks each including a repeating unit having an aromatic ring and 2 nd blocks located between 2 1 st blocks and having a weight average molecular weight of 17 ten thousand or more with the current collector 100 having the coating layer 102 including conductive carbon. As described above, in the electrode 1000 according to embodiment 1, the active material layer 110 having the binder 113 containing the block copolymer is in contact with the coating layer 102 containing conductive carbon. As a result, in the electrode 1000 according to embodiment 1, the adhesion between the active material layer 110 and the current collector 100 can be improved by the interaction between the aromatic ring of the block copolymer contained in the binder 113 and the conductive carbon. Since the adhesion between the active material layer 110 and the current collector 100 is improved, the peel strength between the active material layer 110 and the current collector 100 tends to be improved.
As described above, electrode 1000 in embodiment 1 includes active material layer 110 and current collector 100. Hereinafter, the active material layer 110 and the current collector 100 will be described in detail.
[ active Material layer ]
The active material layer 110 in embodiment 1 includes a solid electrolyte 111, an active material 112, and a binder 113. Hereinafter, the solid electrolyte 111, the active material 112, and the binder 113 will be described in detail.
< adhesive >
As described above, the adhesive 113 contains a block copolymer including 2 1 st blocks composed of repeating units having aromatic rings and 2 nd blocks located between the 2 1 st blocks. In the 1 st block, the repeating units having aromatic rings are arranged continuously. The repeating unit refers to a molecular structure derived from a monomer, and is sometimes referred to as a structural unit. The block copolymer has a sequence of, for example, 2 1 st blocks and 12 nd blocks constituting a triblock. The block copolymer is, for example, an ABA type triblock copolymer. In the triblock copolymer, the a block corresponds to the 1 st block and the B block corresponds to the 2 nd block. The 1 st block functions as a hard segment, for example. The 2 nd block functions, for example, as a soft segment.
In the present disclosure, an aromatic ring refers to a cyclic structure having aromaticity. Examples of the aromatic ring contained in the 1 st block include benzene aromatic rings such as benzene ring and naphthalene ring, and the like, and the aromatic ring is a tall and erect ring Non-benzene aromatic rings such as a ring, heteroaromatic rings such as a pyridine ring and a pyrrole ring, and the like.
Examples of the polymer constituting the 1 st block include polystyrene, polyphenyl methacrylate, benzyl polymethacrylate, polyphenylene, polyaryletherketone, polyarylethersulfone, and polyphenylene oxide. In the 1 st block, the repeating unit having an aromatic ring contains a repeating unit derived from, for example, styrene. In the present disclosure, a triblock copolymer in which the 1 st block contains a repeating unit derived from styrene is sometimes referred to as a styrenic triblock copolymer.
The compositions of the 2 1 st blocks contained in the block copolymer may be the same as or different from each other. The polymerization degrees of the 2 1 st blocks may be the same as or different from each other.
The 2 nd block comprises repeating units derived, for example, from a conjugated diene. Examples of the conjugated diene include butadiene and isoprene. The repeating units from the conjugated diene may be hydrogenated. That is, the repeating unit derived from the conjugated diene may or may not have an unsaturated bond such as a carbon-carbon double bond. The 2 nd block is composed of, for example, repeating units derived from a conjugated diene.
The block copolymer contained in the adhesive 113 may be a styrene-based triblock copolymer. Examples of the styrene-based triblock copolymer include a styrene-ethylene/butylene-styrene block copolymer (SEBS), a styrene-ethylene/propylene-styrene block copolymer (SEPS), a styrene-ethylene/propylene-styrene block copolymer (SEEPS), a styrene-butadiene-styrene block copolymer (SBS), and a styrene-isoprene-styrene block copolymer (SIS). These styrenic triblock copolymers are sometimes referred to as styrenic thermoplastic elastomers. These styrenic triblock copolymers tend to be soft and have high strength. Therefore, when the binder 113 contains a styrene-based triblock copolymer, the peel strength between the active material layer 110 and the current collector 100 in the electrode 1000 tends to be further improved.
Block copolymer contained in adhesive 113May be a hydride. The term "hydrogenated compound" means a copolymer obtained by hydrogenating unsaturated bonds such as carbon-carbon double bonds contained in a block copolymer. In particular, in the 2 nd block of the block copolymer, the repeating units derived from the conjugated diene may be hydrogenated. In the present disclosure, a copolymer obtained by hydrogenating a styrene-based triblock copolymer having an unsaturated bond such as a carbon-carbon double bond is sometimes referred to as a hydrogenated styrene-based triblock copolymer. The hydrogenation rate of the block copolymer may be 90% or more, 95% or more, or 99% or more. The hydrogenation ratio of the block copolymer means a ratio of the number of bonds changed from carbon-carbon double bonds to single bonds by hydrogenation to the number of carbon-carbon double bonds contained in the block copolymer before hydrogenation. The hydrogenation rate of the block copolymer can be improved by proton nuclear magnetic resonance 1 H NMR) determination.
Examples of the hydrogenated styrene triblock copolymer include a styrene-ethylene/butylene-styrene block copolymer (SEBS), a styrene-ethylene/propylene-styrene block copolymer (SEPS), and a styrene-ethylene/propylene-styrene block copolymer (SEEPS). That is, the block copolymer contained in the adhesive 113 may include at least 1 block copolymer selected from the group consisting of SEBS, SEPS, and SEEPS. There is a tendency that hydrogenated styrenic triblock copolymers are softer and have higher strength. Therefore, when the binder 113 contains a hydrogenated styrene triblock copolymer, the peel strength between the active material layer 110 and the current collector 100 in the electrode 1000 tends to be further improved.
The block copolymer contained in the adhesive 113 may contain a modifying group. The modifying group refers to a functional group in which all of the repeating units contained in the polymer chain, a part of the repeating units contained in the polymer chain, or a terminal portion of the polymer chain is chemically modified. The modifying group may be introduced into the polymer chain by substitution reaction, addition reaction, or the like. The modifying group contains an element such as O, N having high electronegativity, si having low electronegativity, or the like. According to the modifying group containing such an element, the block copolymer can be given polarity. Examples of the modifying group include a carboxylic acid group, an acid anhydride group, an acyl group, a hydroxyl group, a sulfo group, a sulfanyl group, a phosphoric acid group, a phosphonic acid group, an isocyanate group, an epoxy group, a silyl group, an amino group, a nitrile group, and a nitro group. Specific examples of the acid anhydride group are maleic anhydride groups. When the block copolymer contains a modifying group, interaction between the binder 113 and the metal contained in the current collector 100 may occur. Due to this interaction, the peel strength between the active material layer 110 and the current collector 100 in the electrode 1000 tends to be further improved.
The block copolymer contained in the adhesive 113 may contain a modifying group as a nitrogen component. The modified group containing a nitrogen component is a nitrogen-containing functional group, and examples thereof include an amino group such as an amine compound. The position of the modifying group may be at the end of the polymer chain. The block copolymer contained in the adhesive 113 may be, for example, a terminal amine-modified hydrogenated styrenic triblock copolymer.
In the adhesive 113, the weight average molecular weight (M w ) Is more than 17 ten thousand. The weight average molecular weight of the block copolymer may be 20 ten thousand or more, 23 ten thousand or more, 30 ten thousand or more, or 40 ten thousand or more. The upper limit of the weight average molecular weight of the block copolymer is not particularly limited, and is, for example, 100 ten thousand. The weight average molecular weight can be determined by Gel Permeation Chromatography (GPC) measurement using polystyrene as a standard sample. In other words, the weight average molecular weight is a value obtained by conversion with polystyrene. Chloroform may be used as the eluent in the GPC measurement. When 2 or more peaks are observed in the GPC chart, the weight average molecular weight calculated from the entire peak range including each peak can be regarded as the weight average molecular weight of the block copolymer.
The dispersibility of the block copolymer in the adhesive 113 may be 1.6 or less, or may be 1.5 or less, or may be 1.4 or less, or may be 1.3 or less. The lower limit of the dispersity of the block copolymer is not particularly limited, and is, for example, 1.1. The dispersity of the block copolymer refers to the weight average molecular weight (M w ) Relative to the number average molecular weight (M n ) Ratio (M) w /M n ). The number average molecular weight of the block copolymer can be determined by GPC as described hereinabove with respect to the weight average molecular weight To determine. With respect to the block copolymer, in the case where the dispersity is 1.6 or less and the molecular weight distribution is narrow, interactions are generated more uniformly among the polymer chains of the plurality of block copolymers. This tends to further increase the peel strength between the active material layer 110 and the current collector 100 in the electrode 1000.
In the block copolymer of the adhesive 113, the average polymerization degree of the 1 st block may be 210 or more, 230 or more, 250 or more, 270 or more, 280 or more, 300 or more, 350 or more, 400 or more, or 460 or more. The upper limit of the average polymerization degree of the 1 st block is not particularly limited, and is, for example, 1000. With the structure in which the average polymerization degree of the 1 st block is 210 or more, the adhesive strength between the active material layer 110 and the current collector 100 tends to be further improved in the electrode 1000 according to embodiment 1.
In the block copolymer of the adhesive 113, the average polymerization degree of the 1 st block is an average value of polymerization degrees per 1 st block. For example, in the case where the block copolymer is an ABA type triblock copolymer, the average polymerization degree of the 1 st block corresponds to the average value of the number of repeating units in 2 a blocks contained in 1 polymer chain constituting the triblock copolymer. In the case where the block copolymer is a triblock copolymer of the ABA type, the average degree of polymerization of the 1 st block may be based on the number average molecular weight (M n ) Mole fraction of repeating units having aromatic rings in Block copolymerMolecular weight of repeating units having aromatic rings (M 1 ) And the molecular weight (M) of the repeating units constituting the 2 nd block 2 ) And is calculated from the following formula (i).
[ number 1]
In the block copolymer, the aromatic ring is containedIn the case where the ratio of the polymerization degree of the repeating units to the polymerization degree of the repeating units constituting the 2 nd block is m: n, the molar fraction of the repeating units having an aromatic ring in the block copolymerCan pass->To calculate. Molar fraction of repeating units having aromatic rings in Block copolymer +.>For example, proton nuclear magnetic resonance can be used 1 H NMR) measurement.
The adhesive 113 may also contain an adhesive other than the block copolymer, such as a binder that is generally used as an adhesive for a battery. Alternatively, the adhesive 113 may be a block copolymer. In other words, the adhesive 113 may contain only a block copolymer.
Examples of the binder include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene, polypropylene, an aromatic polyamide resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polyhexyl acrylate, polymethacrylic acid, polymethyl methacrylate (PMMA), polyethyl methacrylate, polyhexyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, polyether, polycarbonate, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylene sulfide, hexafluoropropylene, styrene butadiene rubber, carboxymethyl cellulose, and ethylcellulose. As the binder, a copolymer synthesized using 2 or more monomers selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, butadiene, isoprene, styrene, pentafluoropropene, fluoromethyl vinyl ether, acrylic acid, and hexadiene can also be used. The number of these may be 1 alone or 2 or more.
The adhesive may contain an elastomer from the viewpoint of excellent adhesion. The elastomer means a polymer having rubber elasticity. The elastomer used as the adhesive 113 may be a thermoplastic elastomer or a thermosetting elastomer. Examples of the elastomer include Butadiene Rubber (BR), isoprene Rubber (IR), chloroprene Rubber (CR), acrylonitrile-butadiene rubber (NBR), hydrogenated Isoprene Rubber (HIR), hydrogenated butyl rubber (HIIR), hydrogenated nitrile rubber (HNBR), and Acrylate Butadiene Rubber (ABR), in addition to the above-mentioned styrene-based elastomer. Mixtures comprising more than 2 elastomers selected from them may also be used.
< active Material >
In embodiment 1, the active material 112 is a positive electrode active material or a negative electrode active material. In the case where the active material 112 is a positive electrode active material, the electrode 1000 can be used as a positive electrode. In the case where the active material 112 is a negative electrode active material, the electrode 1000 can be used as a negative electrode.
The positive electrode active material as the active material 112 is, for example, a material having a property of occluding and releasing metal ions (for example, lithium ions). Examples of the positive electrode active material are lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxysulfides, transition metal oxynitrides, and the like. Examples of lithium-containing transition metal oxides are Li (Ni, co, al) O 2 、Li(Ni,Co,Mn)O 2 、LiCoO 2 Etc. The active material 112 contains, for example, a transition metal oxide containing lithium. In the case where a transition metal oxide containing lithium is used as the active material 112, the manufacturing cost of the electrode 1000 and the battery can be reduced, and the average discharge voltage of the battery can be increased.
The active material 112 may comprise lithium nickel cobalt manganate. The active material 112 is adapted to increase the energy density of the battery. For example, the positive electrode active material as the active material 112 may be Li (Ni, co, mn) O 2 。
The negative electrode active material as the active material 112 is, for example, a material having a property of occluding and releasing metal ions (for example, lithium ions). Examples of the anode active material are a metal material, a carbon material, an oxide, a nitride, a tin compound, a silicon compound, and the like. The metal material may be a simple metal or an alloy. Examples of the metal material are lithium metal, lithium alloy, and the like. Examples of carbon materials are natural graphite, coke, graphitized mesophase carbon, carbon fibers, spherical carbon, artificial graphite, amorphous carbon, and the like. By using silicon (Si), tin (Sn), a silicon compound, a tin compound, or the like as the active material 112, the capacity density of the battery can be improved. By using an oxide compound containing titanium (Ti) or niobium (Nb) as the active material 112, the safety of the battery can be improved.
< solid electrolyte >
In embodiment mode 1, as the solid electrolyte 111, a sulfide solid electrolyte, an oxide solid electrolyte, a halide solid electrolyte, a polymer solid electrolyte, a complex hydride solid electrolyte, or the like can be used. The solid electrolyte 111 may also include a halide solid electrolyte.
In the present disclosure, the "oxide solid electrolyte" refers to a solid electrolyte containing oxygen. The oxide solid electrolyte may further contain anions other than sulfur and halogen elements as anions other than oxygen.
In the present disclosure, the "halide solid electrolyte" refers to a solid electrolyte that contains a halogen element and does not contain sulfur. In the present disclosure, the sulfur-free solid electrolyte refers to a solid electrolyte represented by a composition formula containing no sulfur element. Therefore, an extremely small amount of sulfur component, for example, a solid electrolyte having 0.1 mass% or less of sulfur is included in the solid electrolyte containing no sulfur. The halide solid electrolyte may further contain oxygen as an anion other than the halogen element.
As the sulfide solid electrolyte, for example, li can be used 2 S-P 2 S 5 、Li 2 S-SiS 2 、Li 2 S-B 2 S 3 、Li 2 S-GeS 2 、Li 3.25 Ge 0.25 P 0.75 S 4 、Li 10 GeP 2 S 12 Etc. LiX and Li may be added to them 2 O、MO q 、Li p MO q Etc. The element X in "LiX" is at least 1 element selected from the group consisting of F, cl, br, and I. "MO" of q "and" Li p MO q The element M in the "is at least 1 element selected from the group consisting of P, si, ge, B, al, ga, in, fe and Zn. "MO" of q "and" Li p MO q P and q in "are each independently a natural number.
As the sulfide solid electrolyte, for example, li may also be used 2 S-P 2 S 5 Is a glass ceramic. In Li 2 S-P 2 S 5 LiX and Li may be added to the glass ceramic 2 O、MO q 、Li p MO q For example, 2 or more kinds selected from LiCl, liBr and LiI may be added. Li (Li) 2 S-P 2 S 5 Since the glass ceramic is a relatively soft material, the glass ceramic contains Li 2 S-P 2 S 5 The solid electrolyte sheet is made of glass ceramic, and a battery having higher durability can be produced.
As the oxide solid electrolyte, for example, liTi can be used 2 (PO 4 ) 3 NASICON type solid electrolyte represented by element substitution body thereof, (LaLi) TiO 3 Perovskite-based solid electrolyte comprising Li 14 ZnGe 4 O 16 、Li 4 SiO 4 、LiGeO 4 Lisicon type solid electrolyte represented by element substitution body thereof, and lithium ion secondary battery 7 La 3 Zr 2 O 12 Garnet-type solid electrolyte represented by its element substitution body, and Li 3 PO 4 And N substitution thereof, liBO 2 、Li 3 BO 3 Equal Li-B-O compound as base and Li is added 2 SO 4 、Li 2 CO 3 And the like, and glass ceramics, and the like.
The halide solid electrolyte contains, for example, li, M1, and X. M1 is at least 1 element selected from the group consisting of metal elements other than Li and metalloid elements. X is at least 1 element selected from the group consisting of F, cl, br and I. The halide solid electrolyte has high thermal stability, and thus can improve the safety of the battery. In addition, the halide solid electrolyte contains no sulfur, and thus can suppress the generation of hydrogen sulfide gas. On the other hand, the halide solid electrolyte is a hard and brittle material as compared with the sulfide solid electrolyte. According to the electrode 1000 of embodiment 1, even when a halide solid electrolyte is used, the peel strength between the active material layer 110 and the current collector 100 can be more effectively improved.
In the present disclosure, the "metalloid element" is B, si, ge, as, sb and Te.
In the present disclosure, the "metal element" is all elements contained in groups 1 to 12 of the periodic table of elements other than hydrogen, and all elements contained in groups 13 to 16 of the periodic table of elements other than B, si, ge, as, sb, te, C, N, P, O, S and Se.
That is, in the present disclosure, the "metalloid element" and the "metal element" are element groups capable of becoming cations when an inorganic compound is formed with a halogen element.
For example, the halide solid electrolyte may be a material represented by the following composition formula (1).
Li α M1 β X γ Formula (1)
In the above-mentioned composition formula (1), α, β and γ are each independently a value greater than 0. Gamma may be 4, 6, etc.
With the above configuration, the ionic conductivity of the halide solid electrolyte is improved, and thus the ionic conductivity of the electrode 1000 in embodiment 1 can be improved. Therefore, when the electrode 1000 in embodiment 1 is used in a battery, the cycle characteristics of the battery can be further improved.
In the above composition formula (1), the element M1 may contain Y (=yttrium). That is, the halide solid electrolyte may contain Y as a metal element.
The halide solid electrolyte containing Y can be represented, for example, by the following composition formula (2).
Li a Me b Y c X 6 Formula (2)
In formula (2), a, b and c may satisfy a+mb+3c=6, and c>0. The element Me is at least 1 element selected from the group consisting of metal elements and metalloid elements other than Li and Y. m represents the valence of the element Me. When the element Me includes a plurality of elements, mb is a total value of products of the composition ratio of each element and the valence of the element. For example, me includes element Me1 and element Me2, and the composition ratio of element Me1 is b 1 Valence number of element Me1 is m 1 The composition ratio of the element Me2 is b 2 Valence number of element Me2 is m 2 In the case of (2), mb is defined by m 1 b 1 +m 2 b 2 And (3) representing. In the above-mentioned composition formula (2), the element X is at least 1 element selected from the group consisting of F, cl, br, and I.
The element Me may be, for example, at least 1 element selected from the group consisting of Mg, ca, sr, ba, zn, sc, al, ga, bi, zr, hf, ti, sn, ta, gd and Nb.
As the halide solid electrolyte, the following materials can be used, for example. The ion conductivity of the solid electrolyte 111 is further improved according to the following materials, and therefore the ion conductivity of the electrode 1000 in embodiment 1 can be further improved. Thus, the electrode 1000 in embodiment 1 can further improve the cycle characteristics of the battery.
The halide solid electrolyte may be a material represented by the following composition formula (A1).
Li 6-3d Y d X 6 Formula (A1)
In the composition formula (A1), the element X is at least 1 element selected from the group consisting of Cl, br, and I. In the composition formula (A1), d satisfies 0< d <2.
The halide solid electrolyte may be a material represented by the following composition formula (A2).
Li 3 YX 6 Formula (A2)
In the composition formula (A2), the element X is at least 1 element selected from the group consisting of Cl, br, and I.
The halide solid electrolyte may be a material represented by the following composition formula (A3).
Li 3-3δ Y 1+δ Cl 6 Formula (A3)
In the composition formula (A3), δ satisfies 0< δ.ltoreq.0.15.
The halide solid electrolyte may be a material represented by the following composition formula (A4).
Li 3-3δ Y 1+δ Br 6 Formula (A4)
In the composition formula (A4), δ satisfies 0< δ.ltoreq.0.25.
The halide solid electrolyte may be a material represented by the following composition formula (A5).
Li 3-3δ+a Y 1+δ-a Me a Cl 6-x-y Br x I y Formula (A5)
In the composition formula (A5), the element Me is at least 1 element selected from the group consisting of Mg, ca, sr, ba and Zn.
In addition, in the above composition formula (A5), the following is satisfied:
-1<δ<2，
0<a<3，
0<(3-3δ+a)，
0<(1+δ-a)，
0≤x≤6，
y is more than or equal to 0 and less than or equal to 6
(x+y)≤6。
The halide solid electrolyte may be a material represented by the following composition formula (A6).
Li 3-3δ Y 1+δ-a Me a Cl 6-x-y Br x I y Formula (A6)
In the composition formula (A6), the element Me is at least 1 element selected from the group consisting of Al, sc, ga, and Bi.
In addition, in the above composition formula (A6), the following is satisfied:
-1<δ<1，
0<a<2，
0<(1+δ-a)，
0≤x≤6，
y is more than or equal to 0 and less than or equal to 6
(x+y)≤6。
The halide solid electrolyte may be a material represented by the following composition formula (A7).
Li 3-3δ-a Y 1+δ-a Me a Cl 6-x-y Br x I y Formula (A7)
In the composition formula (A7), the element Me is at least 1 element selected from the group consisting of Zr, hf, and Ti.
In addition, in the above composition formula (A7), the following is satisfied:
-1<δ<1，
0<a<1.5，
0<(3-3δ-a)，
0<(1+δ-a)，
0≤x≤6，
Y is more than or equal to 0 and less than or equal to 6
(x+y)≤6。
The halide solid electrolyte may be a material represented by the following composition formula (A8).
Li 3-3δ-2a Y 1+δ-a Me a Cl 6-x-y Br x I y Formula (A8)
In the composition formula (A8), the element Me is at least 1 element selected from the group consisting of Ta and Nb.
In addition, in the above composition formula (A8), the following is satisfied:
-1<δ<1，
0<a<1.2，
0<(3-3δ-2a)，
0<(1+δ-a)，
0≤x≤6，
y is more than or equal to 0 and less than or equal to 6
(x+y)≤6。
The halide solid electrolyte may be a compound containing Li, M2, O (oxygen), and X2. The element M2 includes, for example, at least 1 element selected from the group consisting of Nb and Ta. X2 is at least 1 element selected from the group consisting of F, cl, br, and I.
IncludedThe compounds of Li, M2, X2 and O (oxygen) may be represented by the following formula: li (Li) x M2O y X2 5+x―2y And (3) representing. Here, x may satisfy 0.1<x<7.0.y may satisfy 0.4<y<1.9。
As the halide solid electrolyte, more specifically, for example, li can be used 3 Y(Cl,Br,I) 6 、Li 2.7 Y 1.1 (Cl,Br,I) 6 、Li 2 Mg(F,Cl,Br,I) 4 、Li 2 Fe(F,Cl,Br,I) 4 、Li(Al,Ga,In)(F,Cl,Br,I) 4 、Li 3 (Al,Ga,In)(F,Cl,Br,I) 6 、Li 3 (Ca,Y,Gd)(Cl,Br,I) 6 、Li 2.7 (Ti,Al)F 6 、Li 2.5 (Ti,Al)F 6 、Li(Ta,Nb)O(F,Cl) 4 Etc. In the present disclosure, when an element In the formula is expressed as "(Al, ga, in)" In this way, the expression indicates at least 1 element selected from the group of elements In parentheses. That is, "(Al, ga, in)" is synonymous with "at least 1 element selected from the group consisting of Al, ga, and In". The same applies to other elements.
As the polymer solid electrolyte, for example, a compound formed of a polymer compound and a lithium salt can be used. The polymer compound may have an ethylene oxide structure. The polymer compound having an ethylene oxide structure can contain a large amount of lithium salt. Therefore, the ion conductivity can be further improved. As lithium salt, liPF can be used 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiSO 3 CF 3 、LiN(SO 2 F) 2 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiN(SO 2 CF 3 )(SO 2 C 4 F 9 )、LiC(SO 2 CF 3 ) 3 Etc. The lithium salt may be used alone or in combination of 2 or more.
As the complex hydride solid electrolyte, for example, liBH can be used 4 -LiI、LiBH 4 -P 2 S 5 Etc.
< active Material layer >
As described above, the active material layer 110 includes the solid electrolyte 111. With this structure, the ion conductivity in the active material layer 110 is improved, and the battery can operate at a high output.
When the solid electrolyte 111 contained in the active material layer 110 has a particle shape (for example, spherical shape), the median particle diameter of the solid electrolyte 111 may be 100 μm or less. When the median particle diameter of the solid electrolyte 111 is 100 μm or less, the active material 112 and the solid electrolyte 111 can be well dispersed in the active material layer 110. This improves the charge/discharge characteristics of the battery.
The median particle diameter of the solid electrolyte 111 contained in the active material layer 110 may be smaller than the median particle diameter of the active material 112. Thus, the solid electrolyte 111 and the active material 112 can be well dispersed.
The median particle diameter of the active material 112 may be 0.1 μm or more and 100 μm or less. When the median particle diameter of the active material is 0.1 μm or more, the active material 112 and the solid electrolyte 111 can be well dispersed in the active material layer 110. As a result, the charge-discharge characteristics of the battery using the electrode 1000 are improved. When the median particle diameter of the active material 112 is 100 μm or less, the lithium diffusion rate in the active material increases. Therefore, the battery using the electrode 1000 can operate at high output power.
The median particle diameter is a particle diameter at which the cumulative volume in the volume-based particle size distribution is 50%. The volume-based particle size distribution can be determined by laser diffraction scattering. The same applies to the other materials described below.
In the active material layer 110, 30.ltoreq.v1.ltoreq.95 may be satisfied with respect to the volume ratio "v1:100-v1" of the active material 112 to the solid electrolyte 111. v1 represents the volume ratio of the active material 112 when the total volume of the active material 112 and the solid electrolyte 111 contained in the active material layer 110 is 100. When v1 is not less than 30%, sufficient energy density is easily ensured for the battery. When v1 is not more than 95, the battery can be operated at a high output more easily.
The thickness of the active material layer 110 may be 10 μm or more and 500 μm or less. When the thickness of the active material layer 110 is 10 μm or more, a sufficient energy density can be easily ensured for the battery. When the thickness of the active material layer 110 is 500 μm or less, the battery can more easily operate at high output.
The active material 112 may be coated with a coating material in order to reduce the interface resistance with the solid electrolyte 111. As the coating material, a material having low electron conductivity can be used. As the coating material, an oxide solid electrolyte, or the like can be used.
As the oxide material for the coating material, siO may be used 2 、Al 2 O 3 、TiO 2 、B 2 O 3 、Nb 2 O 5 、WO 3 、ZrO 2 Etc.
As the oxide solid electrolyte for the coating material, for example, liNbO can be used 3 Equal Li-Nb-O compound, liBO 2 Li (lithium ion battery) 3 BO 3 Equal Li-B-O compound, liAlO 2 Equal Li-Al-O compound, li 4 SiO 4 Equal Li-Si-O compound, li 2 SO 4 Equal Li-S-O compound, li 4 Ti 5 O 12 Equal Li-Ti-O compound, li 2 ZrO 3 Equal Li-Zr-O compound, li 2 MoO 3 Equal Li-Mo-O compound, liV 2 O 5 Equal Li-V-O compound, li 2 WO 4 And Li-W-O compounds. The oxide solid electrolyte has higher ionic conductivity and higher high-potential stability. Therefore, by using the oxide solid electrolyte as the coating material, the charge-discharge efficiency of the battery can be further improved.
The coating material for coating the active material 112 may contain the oxide solid electrolyte and the halide solid electrolyte. The active material layer 110 may include an active material 112 coated with the coating material and a sulfide solid electrolyte as the solid electrolyte 111.
The ratio of the binder 113 to the solid electrolyte 111 in the active material layer 110 may be 0.5 mass% or more and 10 mass% or less, or 1 mass% or more and 6 mass% or less, or 1 mass% or more and 5 mass% or less. When the ratio of the binder 113 to the solid electrolyte 111 is 0.5 mass% or more, more particles of the solid electrolyte 111 tend to be bonded to each other by the binder 113. This can improve the film strength of the active material layer 110. When the ratio of the binder 113 to the solid electrolyte 111 is 10 mass% or less, the contact property between the particles of the solid electrolyte 111 in the active material layer 110 tends to be improved. This can improve the ion conductivity of the active material layer 110.
[ collector ]
The current collector 100 in embodiment 1 has a substrate 101 and a coating layer 102. The coating layer 102 coats the substrate 101 and is in contact with the active material layer 110. The coating layer 102 contains conductive carbon. As described above, with the above-described structure, in the electrode 1000 according to embodiment 1, the interaction between the aromatic ring of the block copolymer contained in the binder 113 in the active material layer 110 and the conductive carbon contained in the coating layer 102 in the current collector 100 occurs. By this interaction, adhesion between the active material layer 110 and the current collector 100 can be improved.
< coating layer >
The coating layer 102 in embodiment 1 may cover the main surface of the substrate 101 as a whole, or may partially cover the main surface of the substrate 101. The "main surface" refers to the surface of the substrate 101 having the largest area. The coating layer 102 is located between the substrate 101 and the active material layer 110, and contacts the substrate 101 and the active material layer 110, respectively. The shape of the coating layer 102 may be dot-like, stripe-like, or the like.
Examples of the conductive carbon contained in the coating layer 102 include graphite such as natural graphite and artificial graphite, carbon black such as Acetylene Black (AB) and Ketjen Black (KB), conductive fibers such as vapor deposition carbon (VGCF (registered trademark)), and Carbon Nanotubes (CNT).
The content of the conductive carbon in the coating layer 102 is not particularly limited, and may be, for example, 5 mass% or more and 80 mass% or less, 10 mass% or more and 60 mass% or less, or 15 mass% or more and 45 mass% or less. When the content of conductive carbon is 5 mass% or more, the conductivity of the coating layer 102 is improved, and thus the battery can have higher output. When the content of conductive carbon is 80 mass% or less, a binder or the like described later is sufficiently present, and thus peeling of the coating layer 102 tends to be suppressed.
The coating layer 102 may contain other elements or components other than conductive carbon. Other elements or components may be added to the coating layer 102 by doping or the like. For example, an unavoidable oxide film or the like may be formed on a part of the surface of the coating layer 102. That is, the coating layer 102 may contain an unavoidable oxide or the like. The coating layer 102 may contain an adhesive. The coating layer 102 containing the adhesive tends to be easily maintained on the substrate 101. The binder is not particularly limited, and the above-mentioned binders can be used. As the binder, for example, a fluorine-based resin such as Polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PVDF) or the like can be used. Since the fluorine-based resin has excellent solvent resistance, peeling of the coating layer 102 can be suppressed even when the active material layer 110 is produced by the wet coating method.
The coating layer 102 can be formed by, for example, sputtering a material of the coating layer 102 onto the surface of the substrate 101. The coating layer 102 may be formed by applying a solution or dispersion of a material containing the coating layer 102 to the surface of the substrate 101. The application of the solution or dispersion may be performed by a gravure coater, a die coater, or the like.
When a solution or dispersion containing the material of the coating layer 102 is applied to the surface of the substrate 101, the coating weight of the material of the coating layer 102 is not particularly limited, and is, for example, 0.01g/m 2 Above and 5g/m 2 Hereinafter, the concentration may be 0.1g/m 2 Above and 3g/m 2 The following is given. At a coating weight of 0.01g/m 2 In the above case, contact between the substrate 101 and the active material layer 110 can be sufficiently prevented, and thusCorrosion of the substrate 101 can be suppressed. At a coating weight of 5g/m 2 In the following case, the resistance of the coating layer 102 is reduced, and the battery can easily operate at high output.
The thickness of the coating layer 102 is not particularly limited, and may be, for example, 0.001 μm or more and 5 μm or less, or 0.1 μm or more and 2 μm or less. When the thickness of the coating layer 102 is 0.001 μm or more, contact between the substrate 101 and the active material layer 110 can be sufficiently prevented, and thus corrosion of the substrate 101 can be suppressed. When the thickness of the coating layer 102 is 5 μm or less, the resistance of the coating layer 102 decreases, and the battery can easily operate at high output.
< substrate >
The substrate 101 has a plate shape, for example. As a material of the substrate 101, a metal or an alloy can be used. Examples of the metal include aluminum, iron, nickel, copper, and the like. Examples of the metal alloy include aluminum alloy and stainless steel (SUS). The substrate 101 may include aluminum or an aluminum alloy.
The substrate 101 may contain aluminum as a main component. The term "the substrate 101 contains aluminum as a main component" means that the content of aluminum in the substrate 101 is 50 mass% or more. Aluminum is a lightweight metal with high electrical conductivity. Therefore, the electrode 1000 including the substrate 101 containing aluminum as a main component can increase the gravimetric energy density of the battery. The substrate 101 containing aluminum as a main component may further contain an element other than aluminum. When the substrate 101 is made of only aluminum, that is, when the content of aluminum in the substrate 101 is 100%, the strength of the substrate 101 may be lowered. Therefore, the substrate 101 may contain an element other than aluminum. The content of aluminum in the substrate 101 may be 99 mass% or less or 90 mass% or less.
The substrate 101 may contain an aluminum alloy. Aluminum alloys are lightweight and have high strength. Therefore, the electrode 1000 including the substrate 101 including the aluminum alloy can realize a battery having both high weight energy density and high durability. The aluminum alloy is not particularly limited, and examples thereof include, al-Cu alloy, al-Mn alloy Al-Mn-Cu alloy, al-Fe-Cu alloy, etc.
As a material of the substrate 101 in embodiment mode 1, an al—mn alloy can be used. The Al-Mn alloy has high strength and excellent formability and corrosion resistance. Therefore, the electrode 1000 including the substrate 101 containing al—mn alloy can improve cycle characteristics of the battery.
The thickness of the substrate 101 is not particularly limited, and may be, for example, 0.1 μm or more and 50 μm or less, or 1 μm or more and 30 μm or less. When the thickness of the substrate 101 is 0.1 μm or more, the strength of the substrate 101 is improved, and therefore breakage of the substrate 101 can be suppressed. When the thickness of the substrate 101 is 50 μm or less, the resistance of the substrate 101 is reduced, and the battery can easily operate at high output.
< collector >
The current collector 100 has a plate-like shape, for example. The thickness of the current collector 100 may be 0.1 μm or more and 1mm or less. When the thickness of the current collector 100 is 0.1 μm or more, the strength of the current collector 100 increases, and therefore breakage of the current collector 100 can be suppressed. When the thickness of the current collector 100 is 1mm or less, the resistance of the electrode 1000 decreases, and the battery can easily operate at high output. That is, by appropriately adjusting the thickness of the current collector 100, a battery can be stably manufactured, and an operation at high output can be performed for the battery.
[ method for manufacturing electrode ]
The electrode 1000 in embodiment 1 can be manufactured by, for example, the following method. First, a dispersion containing the solid electrolyte 111, the active material 112, and the binder 113 for forming the active material layer 110 is prepared. As the dispersion, a slurry obtained by dispersing the solid electrolyte 111, the active material 112, and the binder 113 in a solvent can be used. As the solvent, a solvent that does not react with the solid electrolyte 111, for example, an aromatic hydrocarbon solvent such as toluene can be used. Next, the dispersion is applied to the coating layer 102 of the current collector 100. Examples of the method for applying the dispersion include a die coating method, a gravure coating method, a doctor blade method, a bar coating method, a spray coating method, and an electrostatic coating method. The electrode 1000 can be obtained by drying the obtained coating film to form the active material layer 110. The method of drying the coating film is not particularly limited. For example, the coating film may be heated at a temperature of 80 ℃ or higher for 1 minute or more, whereby the coating film is dried. The drying of the coating film may be performed under a vacuum atmosphere or a reduced pressure atmosphere. The method of forming the active material layer 110 by applying the dispersion to the coating layer 102 may be referred to as a wet coating method.
(embodiment 2)
Embodiment 2 will be described below. The description repeated with embodiment 1 is omitted as appropriate.
Fig. 2 shows a cross-sectional view of a battery 2000 according to embodiment 2.
The battery 2000 in embodiment 2 includes a positive electrode 201, a negative electrode 203, and an electrolyte layer 202.
At least one selected from the positive electrode 201 and the negative electrode 203 is the electrode 1000 in embodiment 1. That is, at least one selected from the positive electrode 201 and the negative electrode 203 includes the active material layer 110 and the current collector 100 described in embodiment 1.
The electrolyte layer 202 is located between the positive electrode 201 and the negative electrode 203.
With the above configuration, the battery 2000 according to embodiment 2 can improve the output characteristics.
As shown in fig. 2, in the battery 2000 in embodiment 2, the positive electrode 201 may be the electrode 1000 in embodiment 1 described above. In this case, the positive electrode 201 includes the active material layer 110 and the current collector 100 described in embodiment 1. Hereinafter, the battery 2000 in which the positive electrode 201 is the electrode 1000 will be described. However, the battery 2000 of embodiment 2 is not limited to the following. In the battery 2000, the negative electrode 203 may be the electrode 1000 in embodiment 1.
With the above configuration, the output characteristics of the battery 2000 can be further improved.
The electrolyte layer 202 is a layer containing an electrolyte material. Examples of the electrolyte material include solid electrolytes. That is, the electrolyte layer 202 may be a solid electrolyte layer. As the solid electrolyte contained in the electrolyte layer 202, the solid electrolyte exemplified as the solid electrolyte 111 of embodiment 1 can be used, and for example, sulfide solid electrolyte, oxide solid electrolyte, halide solid electrolyte, polymer solid electrolyte, complex hydride solid electrolyte, or the like can be used. The solid electrolyte may be a halide solid electrolyte. The halide solid electrolyte has high thermal stability, and thus can improve the safety of the battery 2000.
The electrolyte layer 202 may contain a solid electrolyte as a main component. The electrolyte layer 202 may contain a solid electrolyte in a mass ratio of 70% or more (70% or more) with respect to the entire electrolyte layer 202.
With the above configuration, the charge/discharge characteristics of the battery 2000 can be improved.
The electrolyte layer 202 may contain a solid electrolyte as a main component, and further contains unavoidable impurities, or starting materials, byproducts, decomposition products, and the like used in synthesizing the solid electrolyte.
The electrolyte layer 202 may contain, in addition to the unavoidable impurities, 100% (100% by mass) of a solid electrolyte with respect to the mass ratio of the entire electrolyte layer 202.
With the above configuration, the charge/discharge characteristics of the battery 2000 can be further improved.
The electrolyte layer 202 may contain 2 or more kinds of materials exemplified as solid electrolytes. For example, the electrolyte layer 202 may include a halide solid electrolyte and a sulfide solid electrolyte.
The thickness of the electrolyte layer 202 may be 1 μm or more and 300 μm or less. When the thickness of the electrolyte layer 202 is 1 μm or more, the possibility of short-circuiting between the positive electrode 201 and the negative electrode 203 is reduced. When the thickness of the electrolyte layer 202 is 300 μm or less, the battery 2000 can easily operate at high output. That is, if the thickness of the electrolyte layer 202 is appropriately adjusted, the safety of the battery 2000 can be sufficiently ensured, and the battery 2000 can be operated at a high output.
The shape of the solid electrolyte contained in the battery 2000 is not particularly limited. The shape of the solid electrolyte may be needle-like, spherical, elliptic spherical, or the like. The solid electrolyte may be in the form of particles.
The anode 203 may contain an electrolyte material, for example, may contain a solid electrolyte. As the solid electrolyte, a solid electrolyte exemplified as a material constituting the electrolyte layer 202 can be used. With the above configuration, the ion conductivity (for example, lithium ion conductivity) in the negative electrode 203 is improved, and the battery 2000 can operate at a high output.
The anode 203 contains, for example, a material having a property of occluding and releasing metal ions (e.g., lithium ions) as an anode active material. As the negative electrode active material, the materials exemplified in embodiment 1 above can be used.
The median particle diameter of the anode active material may be 0.1 μm or more and 100 μm or less. When the median particle diameter of the anode active material is 0.1 μm or more, the anode active material and the solid electrolyte can be well dispersed in the anode 203. This improves the charge/discharge characteristics of the battery 2000. When the median particle diameter of the negative electrode active material is 100 μm or less, the lithium diffusion rate in the negative electrode active material increases. Therefore, the battery 2000 can operate at high output power.
The median particle diameter of the anode active material may be larger than the median particle diameter of the solid electrolyte. Thus, the solid electrolyte and the negative electrode active material can be well dispersed.
In the anode 203, 30.ltoreq.v2.ltoreq.95 may be satisfied with respect to the volume ratio "v2:100-v2" of the anode active material to the solid electrolyte. v2 represents the volume ratio of the anode active material when the total volume of the anode active material and the solid electrolyte contained in the anode 203 is 100. When 30.ltoreq.v2 is satisfied, it is easy for the battery 2000 to secure a sufficient energy density. When v2 is equal to or less than 95, the battery 2000 can be operated with high output more easily.
The thickness of the negative electrode 203 may be 10 μm or more and 500 μm or less. When the thickness of the negative electrode 203 is 10 μm or more, a sufficient energy density can be easily ensured for the battery 2000. When the thickness of the negative electrode 203 is 500 μm or less, the battery 2000 can more easily perform an operation at a high output.
The negative electrode active material may be coated with a coating material in order to reduce the interface resistance with the solid electrolyte. As the coating material, a material having low electron conductivity can be used. As the coating material, an oxide solid electrolyte, or the like can be used. As the coating material, the material exemplified in embodiment 1 above can be used.
At least one selected from the electrolyte layer 202 and the negative electrode 203 may contain a binder for the purpose of improving adhesion of particles to each other. As the binder, the materials exemplified in embodiment 1 can be used.
As the adhesive, an elastomer can be used from the viewpoint of excellent adhesion. As the elastic body, the materials exemplified in embodiment 1 can be used. As the binder, 2 or more materials selected from them may be mixed and used. In the case where the binder contains a thermoplastic elastomer, for example, by thermal compression at the time of manufacturing the battery 2000, high filling can be achieved for the electrolyte layer 202 or the anode 203.
In the positive electrode 201, the binder 113 of the active material layer 110 may or may not contain the binder in addition to the block copolymer.
At least one selected from the active material layer 110, the electrolyte layer 202, and the negative electrode 203 of the positive electrode 201 may contain a nonaqueous electrolytic solution, a gel electrolyte, or an ionic liquid for the purpose of facilitating transfer of lithium ions and improving the output characteristics of the battery 2000.
The nonaqueous electrolytic solution contains a nonaqueous solvent and a lithium salt dissolved in the nonaqueous solvent. As the nonaqueous solvent, a cyclic carbonate solvent, a chain carbonate solvent, a cyclic ether solvent, a chain ether solvent, a cyclic ester solvent, a chain ester solvent, a fluorine solvent, or the like can be used. Examples of the cyclic carbonate solvent include ethylene carbonate, propylene carbonate, and butylene carbonate. Examples of the chain carbonate solvent include dimethyl carbonate, methylethyl carbonate, diethyl carbonate, and the like. Examples of the cyclic ether solvent include tetrahydrofuran, 1, 4-dioxane, and 1, 3-dioxolane. Examples of the chain ether solvent include 1, 2-dimethoxyethane and 1, 2-diethoxyethane. Examples of the cyclic ester solvent include gamma-butyrolactone and the like. Examples of the chain ester solvent include methyl acetate and the like. Examples of the fluorine solvent include fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, methylethyl fluorocarbonate, and dimethylene fluorocarbonate. As the nonaqueous solvent, 1 kind of nonaqueous solvent selected from them may be used alone, or a mixture of 2 or more kinds of nonaqueous solvents selected from them may be used.
The nonaqueous electrolytic solution may contain at least 1 fluorine solvent selected from the group consisting of fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, methylethyl fluorocarbonate, and dimethylene fluorocarbonate.
Examples of the lithium salt include LiPF 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiSO 3 CF 3 、LiN(SO 2 F) 2 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiN(SO 2 CF 3 )(SO 2 C 4 F 9 )、LiC(SO 2 CF 3 ) 3 Etc. As the lithium salt, 1 kind of lithium salt selected from them may be used alone, or a mixture of 2 or more kinds of lithium salts selected from them may be used. The concentration of the lithium salt in the nonaqueous electrolytic solution may be 0.5 mol/liter or more and 2 mol/liter or less.
As the gel electrolyte, a material formed by adding a nonaqueous electrolytic solution to a polymer material can be used. Examples of the polymer material include polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, and a polymer having an ethylene oxide bond.
The cation constituting the ionic liquid may be aliphatic chain quaternary cation such as tetraalkylammonium, tetraalkylphosphonium, etc., pyrrolidineClass, morpholine->Class I, imidazoline->Class, tetrahydropyrimidine->Class, piperazine->Class, piperidine->Aliphatic cyclic ammonium, pyridine ∈>Class I, imidazole->Nitrogen-containing heterocyclic aromatic cations such as the like. The anions constituting the ionic liquid may be PF 6 - 、BF 4 - 、SbF 6 - 、AsF 6 - 、SO 3 CF 3 - 、N(SO 2 F) 2 - 、N(SO 2 CF 3 ) 2 - 、N(SO 2 C 2 F 5 ) 2 - 、N(SO 2 CF 3 )(SO 2 C 4 F 9 ) - 、C(SO 2 CF 3 ) 3 - Etc. The ionic liquid may also contain lithium salts.
At least one selected from the active material layer 110 of the positive electrode 201 and the negative electrode 203 may contain a conductive auxiliary agent for the purpose of improving electron conductivity. Examples of the conductive auxiliary agent include graphite such as natural graphite and artificial graphite, carbon black such as acetylene black and ketjen black, conductive fibers such as carbon fibers and metal fibers, conductive powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymers such as polyaniline, polypyrrole and polythiophene. When a carbon material is used as the conductive auxiliary agent, cost reduction can be achieved.
The shape of the battery 2000 may be button type, cylindrical type, square type, sheet type, button type, flat type, laminated type, or the like.
The battery 2000 in embodiment 2 can be manufactured by, for example, the following method. First, a current collector 100, a material for forming the active material layer 110, a material for forming the electrolyte layer 202, a material for forming the negative electrode 203, and a current collector for the negative electrode 203 are prepared, respectively. Using these materials, a laminate in which the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 are sequentially arranged is produced by a known method. Thereby, the battery 2000 can be manufactured.
Examples
The details of the present disclosure will be described below with reference to examples and comparative examples. The electrode and the battery of the present disclosure are not limited to the following examples.
< examples 1 to 1>
[ production of halide solid electrolyte ]
In an argon glove box with a dew point below-60 ℃ in YCl 3 LiCl: libr=1:1:2 molar ratio YCl was weighed as raw material powder 3 LiCl and LiBr. Next, these raw material powders are mixed. The obtained mixture was subjected to firing treatment at 520℃for 2 hours using an electric furnace, thereby obtaining Li as a halide solid electrolyte 3 YBr 2 Cl 4 (hereinafter, referred to as "LYBC").
[ solvent ]
In all the following steps, a commercially available dehydration solvent or a solvent dehydrated by nitrogen bubbling was used as the solvent. The amount of water in the solvent is 10 mass ppm or less.
[ preparation of adhesive solution ]
A solvent is added to the binder to dissolve or disperse the binder in the solvent, thereby preparing a binder solution. The concentration of the binder in the binder solution is adjusted to 5 mass% or more and 6 mass% or less. Next, dehydration treatment was performed by nitrogen bubbling until the moisture content of the binder solution became 10 mass ppm or less.
In example 1-1, p-chlorotoluene was used as a solvent for the binder solution. As the block copolymer constituting the adhesive, SEBS (februn (registered trademark) N504 manufactured by asahi chemical industry, inc.) as a hydrogenated styrene-based thermoplastic elastomer is used. In this SEBS, the molar fraction of the repeating unit having an aromatic ring is 0.21.
[ production of electrode ]
Pulverizing LYBC in a drying chamber with dew point below-40deg.C by using dry jet mill type pulverizer to obtain pulverized LYBC. Then, the adhesive solution was dropped into an argon glove box having a dew point of-60 ℃ or lower, and LYBC was mixed with the adhesive. At this time, LYBC and SEBS are mixed in a mass ratio of LYBC to SEBS=100:3. Further, p-chlorotoluene was added to the obtained mixture, and the solid content concentration was adjusted to 56 mass%. Next, the mixture was kneaded using a rotation/revolution mixer (ARE-310, manufactured by THINKY Co., ltd.) at 1600rpm for 3 minutes, to thereby prepare a slurry. Next, carbon black was coated on an aluminum alloy foil (A1N 30 foil, thickness: 15 μm), thereby producing a current collector having a coating layer. The electrode of example 1-1 was produced by applying a slurry to the coating layer of the current collector and drying the resulting coating film at 100℃for 1 hour under a vacuum atmosphere.
< examples 1 to 2>
Electrodes of examples 1 to 2 were produced in the same manner as in example 1 to 1, except that SEEPS (registered trademark) 4099 was used as a block copolymer constituting the binder. In the SEEPS used in examples 1 to 2, the molar fraction of the repeating units having aromatic rings was 0.21.
< examples 1 to 3>
The electrodes of examples 1 to 3 were produced in the same manner as in example 1 to 1, except that SEPS (clay 2006) was used as the block copolymer constituting the binder. In the SEPS used in examples 1 to 3, the molar fraction of the repeating units having an aromatic ring was 0.24.
< examples 1 to 4>
The electrodes of examples 1 to 4 were produced in the same manner as in example 1 to 1, except that SBS (manufactured by Asahi chemical Co., ltd.) T-411 was used as the block copolymer constituting the binder. In the SBS used in examples 1 to 4, the molar fraction of the repeating units having aromatic rings was 0.17.
Comparative examples 1 to 1 ]
An electrode of comparative example 1-1 was produced in the same manner as in example 1-1 except that an aluminum alloy foil (A1N 30 foil, thickness: 15 μm) was used as a current collector.
Comparative examples 1 to 2
Electrodes of comparative examples 1-2 were produced in the same manner as in example 1-1, except that SEBS (dow gasolin (registered trademark) 8903P) was used as a block copolymer constituting the binder. In the SEBS used in comparative examples 1-2, the molar fraction of the repeating units having an aromatic ring was 0.22.
Comparative examples 1 to 3
Electrodes of comparative examples 1 to 3 were produced in the same manner as in example 1 to 1, except that SBR (tarfefin (registered trademark) 2100R) was used as a polymer constituting the binder. SBR is a random copolymer.
[ determination of weight average molecular weight of Block copolymer, molar fraction of repeating units having aromatic Ring in Block copolymer, and average polymerization degree of 1 st Block of Block copolymer ]
The weight average molecular weight and the like of the block copolymer constituting the adhesive were measured by Gel Permeation Chromatography (GPC) measurement using a high performance GPC apparatus (HLC-832-GPC manufactured by TOSOH Co., ltd.). As the measurement sample, a sample obtained by dissolving a binder in chloroform and filtering with a filter having a pore size of 0.2 μm was used. As a column, 2 Super HM-H manufactured by TOSOH was used. In GPC In the measurement, a differential Refractometer (RI) was used. GPC measurement was carried out at a flow rate of 0.6mL/min and a column temperature of 40 ℃. As a standard sample, monodisperse polystyrene (TOSOH corporation) was used. The number average molecular weight (M) of the block copolymer was determined by GPC measurement n ) Weight average molecular weight (M) w ) Dispersity (M) w /M n )。
The molar fractions of the repeating units having aromatic rings in the block copolymers used in examples 1-1 to 1-4 and comparative examples 1-1 to 1-2 were determined by the following methods. First, proton nuclear magnetic resonance was performed on a measurement sample containing a block copolymer using a nuclear magnetic resonance apparatus (AVANCE 500 manufactured by bruch corporation) 1 H NMR) measurement. As a measurement sample, a method of dissolving a block copolymer in CDCl was used 3 And the obtained sample. CDCl 3 Contains 0.05% TMS. 1 The H NMR measurement was performed at a resonance frequency of 500MHz and a measurement temperature of 23 ℃. From the obtained NMR spectrum, the integral value of the peak from the styrene skeleton and the integral value of the peak from the other skeleton other than the styrene skeleton were determined. Using the determined integral value, the mole fraction of the repeating units having aromatic rings in the block copolymer was determined.
The block copolymers used in examples 1-1 to 1-4 and comparative examples 1-1 to 1-2 were based on the number average molecular weight (M n ) Mole fraction of repeating units having aromatic ringsMolecular weight of repeating units having aromatic rings (M 1 ) And the molecular weight (M) of the repeating units constituting the 2 nd block 2 ) The average polymerization degree of a block (1 st block) composed of repeating units having an aromatic ring was calculated by the following formula (i).
[ number 2]
[ measurement of peel Strength ]
For the electrodes of examples 1-1 to 1-4 and comparative examples 1-1 to 1-3, the peel strength was measured by the following method.
The peel strength was measured in a drying chamber having a dew point of-40℃or lower using a bench tensile compression tester (MCT-2150 manufactured by d.d. Co., ltd.) by the following method. First, electrodes cut to a width of 15mm were adhered to a stent (registered trademark) plate using a double-sided tape. Specifically, the active material layer of the electrode is bonded to the yue plate via a double-sided tape. Next, using a tester, the current collector was peeled from the active material layer fixed by the yue plate under conditions of a peeling angle of 90 ° and a peeling speed of 10 mm/min. After the measurement was started, the measurement value of the first 2mm length peeled off from the current collector was ignored, and then the average value of the measurement values (unit: N) continuously recorded for the active material layer of 8mm length peeled off from the current collector was determined. The average value divided by the width of the electrode was regarded as the peel strength (unit: N/m) between the active material layer and the current collector.
The results of the above measurement are shown in table 1. The types a to F of the binders in table 1 correspond to the polymers described below, respectively.
A: hydrogenated styrene thermoplastic elastomer (SEBS) tap N504
B: hydrogenated styrene thermoplastic elastomer (SEEPS) cartridge 4099
C: hydrogenated styrene thermoplastic elastomer (SEPS) cartridge 2006
D: styrene thermoplastic elastomer (SBS) T-411
E: hydrogenated styrenic thermoplastic elastomer (SEBS) dydron 8903P
F: styrene elastomer (SBR) tarfeban 2100R
Watch (watch)
As can be seen from table 1, in using a polymer having three blocksWhen the sequential block copolymer is used as a binder and carbon black is further used as a material for the coating layer, the weight average molecular weight (M w ) Is related to peel strength. In particular, in the presence of M w In the electrode of the example of the block copolymer of 17 ten thousand or more, the peel strength between the active material layer and the current collector layer was high. From this result, it can be said that the electrode of the example is suitable for improving the peel strength of the active material layer from the current collector.
< example 2-1>
[ preparation of a Dispersion of a halide solid electrolyte ]
Parchlorotoluene was added to LYBC in a drying chamber having a dew point of-40 ℃. The LYBC is pulverized by a wet pulverizer/disperser using a bead mill apparatus, and dispersed in a solvent, thereby obtaining a LYBC dispersion. The concentration of the solid content in the LYBC dispersion was 35% by mass.
[ production of active Material ]
First, a LiNbO-based alloy is prepared 3 Coated Li (Ni, co, mn) O 2 . Next, in an argon glove box with a dew point of-60 ℃ or lower, to pass through LiNbO 3 Coated Li (Ni, co, mn) O 2 LYBC: vgcf=100:7.5:0.41 by mass ratio LiNbO was weighed 3 Coated Li (Ni, co, mn) O 2 LYBC dispersion, vapor phase carbon fiber (VGCF), and p-chlorotoluene. Next, these materials were kneaded using a bench kneader, thereby producing an active material. Li (Ni, co, mn) O in the active material 2 LYBC and LiNbO 3 And (5) coating.
[ production of electrode composite Material ]
The active material, LYBC, and sulfide solid electrolyte Li were weighed in a mass ratio of active material to LYBC to LPS VGCF=85.0:6.4:8.6:1 in an argon glove box having a dew point of-60 ℃ or lower 2 S-P 2 S 5 Is glass ceramic (LPS) and VGCF. They were mixed using a quartz mortar, thereby producing an electrode composite.
[ production of electrode ]
The binder solution was dropped into the electrode composite in an argon glove box with a dew point below-60 ℃ and they were mixed. As the block copolymer constituting the adhesive, SEBS (februn (registered trademark) N504 manufactured by asahi chemical industry, inc.) as a hydrogenated styrene-based thermoplastic elastomer is used. The mixing of the binder solution with the electrode composite was performed at a mass ratio of lybc+lps: sebs=100:2.7. To the obtained mixture was further added mixed xylene to adjust the solid content concentration to 80 mass%. The mixed xylene is a mixed solvent comprising o-xylene, m-xylene, p-xylene and ethylbenzene in a mass ratio of 24:42:18:16. Next, the mixture was kneaded using a rotation/revolution mixer (ARE-310, manufactured by THINKY Co., ltd.) at 1600rpm for 3 minutes, to thereby prepare a slurry. Next, carbon black was coated on an aluminum alloy foil (a 3003 foil, thickness: 15 μm), thereby producing a current collector having a coating layer. The electrode of example 2-1 was produced by applying a slurry to the coating layer of the current collector and drying the resulting coating film at 100℃for 1 hour under a vacuum atmosphere.
< example 2-2>
The electrodes of examples 2-2 were prepared in the same manner as in example 2-1, except that the binder solution and the electrode composite were mixed at a mass ratio of lybc+lps: sebs=100:5.3.
Comparative example 2-1 ]
An electrode of comparative example 2-1 was produced in the same manner as in example 2-1, except that SBR (tarfefin (registered trademark) 2100R) was used as a polymer constituting the binder. SBR is a random copolymer.
Comparative examples 2 to 2 ]
The electrodes of comparative examples 2-2 were prepared in the same manner as in comparative example 2-1 except that the binder solution and the electrode composite were mixed at a mass ratio of lybc+lps: sebs=100:5.3.
[ measurement of peel Strength ]
The electrodes of examples 2-1 to 2-2 and comparative examples 2-1 to 2-2 were subjected to peel strength measurement by the above-described method.
The results of the above measurement are shown in table 2. The types a and F of the resin binders in table 2 correspond to the polymers described below, respectively.
A: hydrogenated styrene thermoplastic elastomer (SEBS) tap N504
F: styrene elastomer (SBR) tarfeban 2100R
TABLE 22
As is clear from table 2, in the electrode of example 2-1, the peel strength of the active material layer and the current collector layer was improved as compared with the electrode of comparative example 2-1 in which the ratio of the binder to the solid electrolyte was the same. It was also found that in the electrode of example 2-2, the peel strength of the active material layer and the collector layer was improved as compared with the electrode of comparative example 2-2 in which the ratio of the binder to the solid electrolyte was the same. As is clear from table 2, when a block copolymer having a triblock sequence and a weight average molecular weight of 17 ten thousand or more is used as a binder and carbon black is further used as a material of the coating layer, the peel strength between the active material layer and the current collector layer is improved. From this result, it can be said that the electrode of the example is suitable for improving the peel strength of the active material layer from the current collector.
< discussion >
As is clear from a comparison between the results of example 1-1 and the results of comparative example 1-1 shown in table 1, when conductive carbon is used as the material of the coating layer, the peel strength between the active material layer and the current collector layer is improved.
As is clear from a comparison of the results of examples 1-1 to 1-4 shown in Table 1 with the results of comparative examples 1-2 and 1-3, when a block copolymer having a triblock sequence and a weight average molecular weight of 17 ten thousand or more was used as a binder, the peel strength of the active material layer and the current collector layer was improved.
From the above results, it was confirmed that the electrode of the present disclosure is suitable for suppressing the peeling of the active material layer from the current collector. The electrode of the present disclosure is an electrode including an active material layer and a current collector,
the active material layer includes an active material, a solid electrolyte, and a binder; the current collector has a substrate and a coating layer which is coated on the substrate and is in contact with the active material layer,
the adhesive contains a block copolymer comprising 2 1 st blocks each comprising a repeating unit having an aromatic ring and 2 nd blocks located between 2 of the 1 st blocks,
the weight average molecular weight of the block copolymer is 17 ten thousand or more,
The coating layer contains conductive carbon.
Industrial applicability
The electrode of the present disclosure may be used, for example, in all-solid lithium ion secondary batteries and the like.
Description of the reference numerals
100. Current collector
101. Substrate board
102. Coating layer
110. Active material layer
111. Solid electrolyte
112. Active substances
113. Adhesive agent
201. Positive electrode
202. Electrolyte layer
203. Negative electrode
1000. Electrode
2000. Battery cell
Claims (11)
1. An electrode comprising an active material layer and a current collector,
the active material layer includes an active material, a solid electrolyte, and a binder; the current collector has a substrate and a coating layer that covers the substrate and is in contact with the active material layer,
the adhesive contains a block copolymer comprising 21 st blocks composed of repeating units having aromatic rings and 2 nd blocks located between 21 st blocks,
the weight average molecular weight of the block copolymer is 17 ten thousand or more,
the coating layer contains conductive carbon.
2. The electrode according to claim 1, wherein the average degree of polymerization of the 1 st block is 210 or more.
3. The electrode of claim 1 or 2, the 2 nd block comprising repeat units from a conjugated diene.
4. The electrode according to claim 1 to 3, wherein the block copolymer is a triblock copolymer,
The repeating unit having the aromatic ring includes a repeating unit derived from styrene.
5. The electrode of claim 4, the block copolymer being a hydride.
6. The electrode according to any one of claims 1 to 5, the block copolymer comprising at least 1 block copolymer selected from the group consisting of styrene-ethylene/butylene-styrene block copolymer, SEBS, styrene-ethylene/propylene-styrene block copolymer, SEPS, and styrene-ethylene/propylene-styrene block copolymer, SEEPS.
7. The electrode of any one of claims 1 to 6, the substrate comprising aluminum or an aluminum alloy.
8. The electrode according to any one of claims 1 to 7, wherein the active material comprises a transition metal oxide containing lithium.
9. The electrode of claim 8, the active material comprising nickel cobalt lithium manganate.
10. A battery comprising a positive electrode, a negative electrode, and an electrolyte layer between the positive electrode and the negative electrode,
at least one selected from the positive electrode and the negative electrode is the electrode according to any one of claims 1 to 9.
11. The battery of claim 10, the positive electrode being the electrode.
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| PCT/JP2022/017374 WO2022249776A1 (en) | 2021-05-27 | 2022-04-08 | Electrode and battery |
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| JP2579154B2 (en) * | 1987-01-21 | 1997-02-05 | 旭化成工業株式会社 | Non-aqueous secondary battery |
| JP2010262764A (en) | 2009-04-30 | 2010-11-18 | Toyota Motor Corp | Slurry for forming positive-electrode mixture layer, and positive-electrode mixture layer |
| JP5652322B2 (en) * | 2011-05-17 | 2015-01-14 | 日本ゼオン株式会社 | Manufacturing method of all-solid-state secondary battery |
| JP5806335B2 (en) | 2012-01-20 | 2015-11-10 | トヨタ自動車株式会社 | Electrode body and manufacturing method thereof |
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| JP6941808B2 (en) | 2017-02-03 | 2021-09-29 | パナソニックＩｐマネジメント株式会社 | All solid state battery |
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